CN110551154B

CN110551154B - Phosphorus-containing bicyclic compound and preparation method and application thereof

Info

Publication number: CN110551154B
Application number: CN201910752883.4A
Authority: CN
Inventors: 张玉祥; 张庆云; 丁欢达; 陈志宽
Original assignee: Ningbo Dinghao Photoelectric Material Technology Co ltd; Ningbo Lumilan Advanced Materials Co Ltd
Current assignee: Ningbo Dinghao Photoelectric Material Technology Co ltd; Ningbo Lumilan Advanced Materials Co Ltd
Priority date: 2019-08-15
Filing date: 2019-08-15
Publication date: 2021-09-24
Anticipated expiration: 2039-08-15
Also published as: CN110551154A

Abstract

The invention belongs to the technical field of electroluminescent materials, and particularly relates to a phosphorus-containing bicyclic compound and a preparation method and application thereof. The phosphorus-containing bicyclic compound provided by the invention has a structure shown as a formula (I) or a formula (II), the compound takes a biphenyl diphosphoryl heptatomic ring as a center, and a proper substituent is introduced into a side chain to form a large electron-deficient conjugated system, and the formed closed-loop structure has excellent electron transmission performance; the compound provided by the invention has proper HOMO energy level and LUMO energy level, can reduce the potential barrier which needs to be overcome by injecting electrons from the cathode to the light-emitting layer, increases the effective injection of electrons, is favorable for reducing the working voltage of a device and improves the light-emitting efficiency of the device; meanwhile, the molecular weight of the material is 550-920, and the molecules have large rigid structures, so that the thermal stability is better, and the material is suitable for the evaporation process of small-molecule organic electroluminescent devices.

Description

Phosphorus-containing bicyclic compound and preparation method and application thereof

Technical Field

The invention belongs to the technical field of electroluminescent materials, and particularly relates to a phosphorus-containing bicyclic compound and a preparation method and application thereof.

Background

Organic light-emitting diodes (OLEDs) are a new flat panel display, and compared with the conventional display, the organic light-emitting diodes have the advantages of fast response, low energy consumption, self-luminescence, wide color gamut, ultra-thinness, foldability, flexibility, capability of manufacturing large-size panels, and the like, and are a novel display technology which is ideal in the future and has the greatest application prospect.

The OLED belongs to a carrier double-injection type light-emitting device, and the light-emitting mechanism is as follows: under the driving of an external electric field, electrons and holes are injected into the organic light emitting layer from the cathode and the anode respectively, and are recombined in the organic light emitting layer to generate excitons, and the excitons radiatively transition back to the ground state and emit light, so that the efficient transport of carriers has an important influence on the light emitting efficiency and the life of the light emitting device.

The good electron transport material can obviously improve the performance of the device. The electron transport material is generally a planar aromatic compound with a large conjugated structure and electron deficiency, has strong electron accepting capability, and can effectively transfer electrons under certain forward bias. The following requirements need to be satisfied as an electron transport material: (1) has good electron transmission characteristics; (2) the cathode has lower electron affinity and is easy to inject electrons from the cathode; (3) the excitation energy is higher than that of the light-emitting layer; (4) the ability to form an exciplex with the light-emitting layer; (5) good film forming property and chemical stability, and difficult crystallization.

The currently available electron transport materials mainly comprise 8-hydroxyquinoline aluminum, oxadiazole, oxazole, imidazole, triazole, nitrogen-containing six-membered heterocyclic ring, organic fluorine, organosilicon, organophosphorus compounds and the like. Having good electron transport properties, it is desirable that the electron mobility of the Electron Transport Material (ETM) should be comparable to the hole mobility of the Hole Transport Material (HTM), while in practice the electron conduction rates of these materials are lower than the hole conduction rates, and this imbalance in carrier transport rates results in a significant degradation of device performance. Therefore, the search for an efficient electron transport material is still an urgent need in the industry.

Disclosure of Invention

Therefore, the technical problem to be solved by the present invention is to overcome the defects of low transmission efficiency, unstable device performance, short lifetime and the like of the electron transport material in the prior art, so as to provide a phosphorus-containing bicyclic compound, a preparation method and an application thereof.

In order to solve the technical problems, the invention adopts the following technical scheme:

a phosphorus-containing bicyclic compound has a structure shown as a formula (I) or a formula (II),

wherein R is₁、R₂Independently selected from hydrogen, deuterium, halogen, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, silyl, aryl or heteroaryl;

ring A, B is independently selected from substituted or unsubstituted benzene rings, fused aromatic rings of C6-C30, fused heterocyclic rings of C6-C30.

Further, said R₁、R₂Independently of one another, is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C30, substituted or unsubstituted alkenyl of C2-C30, substituted or unsubstituted alkynyl of C2-C30, substituted or unsubstituted cycloalkyl of C3-C30, substituted or unsubstituted alkoxy of C1-C30, substituted or unsubstituted silyl of C1-C30, substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C3-C30;

said ring A, B is independently selected from

The ring C is selected from a benzene ring, a biphenyl ring, an adamantane ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a pyrene ring, a perylene ring, a caryophyllene ring, a triphenylene ring, a fluoranthene ring, a pyridine ring, a pyrimidine ring, a pyran ring, a thiopyran ring, a pyrazine ring, a pyridazine ring, a triazine ring, a phthalazine ring, a phenazine ring, a thiophene ring, a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, an indole ring, a carbazole ring, an indolocarbazole ring, a triarylamine ring, a diarylamine ring, a phenanthridine ring, an acridine ring, a perimidine ring, a pteridine ring, a quinazoline ring, a quinoxaline ring, a cinnoline ring, a quinoline ring, a phenanthroline ring or a carboline ring.

Further, it has a molecular structure as shown below:

the invention also provides a preparation method of the phosphorus-containing bicyclic compound, and the synthesis steps of the compounds shown in the formula (I) and the formula (II) comprise:

taking a compound shown in a formula (D) and a compound shown in a formula (E) as starting raw materials, respectively reacting with iodine under an alkaline condition to generate an iodide (F) and an iodide (G), and carrying out coupling reaction on the iodide (F) and the iodide (G) to obtain an intermediate compound (H); forming lithium salt by the intermediate compound (H) under the action of a lithiation reagent, reacting with diphenylphosphonic chloride to obtain an intermediate compound (J), and closing rings at two sides of the intermediate compound (J) under a catalytic condition to obtain a compound shown in a formula (I) or a formula (II);

the synthetic route of the compound shown in the formula (I) is as follows:

the synthetic route of the compound shown in the formula (II) is as follows:

further, the ring closure is carried out in the presence of a Pd reagent.

The invention also provides an application of the phosphorus-containing bicyclic compound as an organic electroluminescent material.

The invention also provides an organic electroluminescent device, wherein at least one functional layer of the organic electroluminescent device contains the phosphorus-containing bicyclic compound.

Further, the functional layer is an electron transport layer, an electron injection layer or a light emitting layer.

Further, the functional layer is an electron transport layer, the electron transport layer material includes a host material and a guest material, and the host material is the phosphorus-containing bicyclic compound.

The invention also provides an electronic product comprising the organic electroluminescent device.

The technical scheme of the invention has the following advantages:

1. the phosphorus-containing bicyclic compound provided by the invention has a structure shown as a formula (I) or a formula (II), and the compound takes a biphenyl diphosphoryheptatomic ring as a center to form a large electron-deficient conjugated system, so that the structure is favorable for electron flow so as to improve the electron mobility of the material, and meanwhile, a proper substituent is introduced into a side chain to enhance the conjugated effect, so that the LUMO energy level is effectively reduced, the electron transfer is facilitated, and in addition, the symmetrical structure of molecules can increase the regularity of molecular stacking so as to improve the carrier mobility of the material. Therefore, the unique conjugated closed-loop structure has excellent electron transmission performance.

2. Compared with the existing phosphorus-containing electron transport materials, the specific bicyclic conjugated structure enables the glass transition temperature of the compound to be increased, so that the material has better film forming property and chemical stability and is not easy to crystallize; the LUMO energy level is reduced, which indicates that the compound has lower electron affinity and is easy to inject electrons from a cathode; the reduction of the LUMO energy level also enables the band gap to be enhanced, and the triplet state energy level is improved, so that the excitation energy of the material is higher than that of the light-emitting layer, an exciplex cannot be formed between the material and the light-emitting layer, and energy loss caused by electron backflow can be prevented; the phosphorus-containing bicyclic compound provided by the invention has proper HOMO energy level and LUMO energy level, can reduce the potential barrier to be overcome by injecting electrons from the cathode to the light-emitting layer, increases the effective injection of electrons, is beneficial to reducing the working voltage of a device and improving the light-emitting efficiency of the device; meanwhile, the molecular weight of the material is between 550-920, and the molecules have large rigid structures, so that the thermal stability is better, and the material can be suitable for the evaporation process of a small-molecule organic electroluminescent device.

3. The phosphorus-containing bicyclic compound provided by the invention is prepared by regulating R₁、R₂The substituent and the structures of the ring A, the ring B and the ring C can ensure that the electron mobility of the material as an electron transport material and the hole mobility of a hole transport material are equivalentAnd balanced carrier transmission is realized, so that the performance and the service life of the device are improved.

4. The organic electroluminescent device provided by the invention contains the phosphorus-containing bicyclic compound, and the OLED device manufactured by using the material as an electron transport material has the advantages of reduced working voltage, improved current efficiency and obvious substitution advantage compared with the traditional electron transport material.

5. The preparation method of the phosphorus-containing bicyclic compound provided by the invention has the advantages of easily obtained starting materials, mild reaction conditions and simple operation steps, and makes large-scale production, popularization and application of the phosphorus-containing bicyclic compound possible.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a schematic diagram of theoretical calculations of the HOMO and LUMO energy levels of a phosphorus-containing bicyclic compound represented by C-7 prepared in example 7 of the present invention.

Fig. 2 is a schematic structural diagram of an organic electroluminescent device provided by the present invention.

Reference numerals:

1-anode, 2-hole injection layer, 3-hole transport layer, 4-luminescent layer, 5-electron transport layer, 6-electron injection layer and 7-cathode.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-1 below:

the synthetic route for the compound of formula C-1 is shown below:

the preparation method of the compound shown as the formula C-1 specifically comprises the following steps:

(1) preparation of intermediate (F-1)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, D-1(130g,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h after the addition, an iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h after the addition, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, the organic phase was washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 600mL of ethanol, and filtered to give 184g (F-1) of a white flaky solid with a yield of 85%.

(2) Preparation of intermediate (H-1)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with the solid intermediate F-1(184g,0.58mol,1.0eq) and 1200mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (240mL,2.5M,0.60mol,1.04eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (135g,0.60mol,1.04eq) is added, stirring is maintained for 1h, nitrobenzene (74g,0.60mol,1.04eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 300mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were then filtered and dried by suction to give 76.2g of a solid (H-1) with a yield of 69%.

(3) Preparation of intermediate (J-1)

Under the protection of nitrogen, adding an intermediate (H-1) (76.2g,0.20mol,1.0eq) and 1000mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (200mL,2.5M,0.50mol,2.5eq), maintaining the reaction for 2H after the addition is finished, then slowly adding diphenylphosphonic chloride (104g,0.44mol,2.2eq), stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. And adding 800mL of water dropwise to quench the reaction, adding 500mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give an off-white solid 74.8g of intermediate (J-1), yield: 60 percent.

(4) Preparation of Compound (C-1)

Under nitrogen protection, a 2L three-necked round bottom flask was charged with intermediate (J-1) (74.8g,0.12mol,1.0eq) and 600mL of dimethylacetamide, followed by pivalic acid (2.45g,0.024mol,0.20eq) and cesium carbonate (78.2g,0.24mol,2.0eq), nitrogen purged for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.77g,0.0024mol,0.02eq), warmed to 150 ℃ for 15h, and HPLC monitored for reaction completion. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, the mixture was filtered through celite, 500mL of dichloromethane was added to the filtrate to extract the filtrate, the organic phase was washed with 1000mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 46.2g of the objective compound (C-1) as an off-white solid, yield: 70 percent.

Elemental analysis: (C)₃₆H₂₄P₂O₂) Theoretical value: c, 78.54; h, 4.39; p, 11.25; o,5.81 found: c, 78.58; h, 4.37; p, 11.24; o, 5.80; MS (ESI) M/z (M +): theoretical value: 550.13, respectively; measured value: 550.32.

example 2

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-2 below:

the synthetic route for the compound of formula C-2 is shown below:

the preparation method of the compound shown as the formula C-2 specifically comprises the following steps:

(1) preparation of intermediate (F-2)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, D-2(139g,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h after the addition, an iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h after the addition, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, the organic phase was washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 650mL of ethanol, and filtered to give 182g (F-2) of a white flaky solid in 81% yield.

(2) Preparation of intermediate (H-2)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with the solid intermediate F-2(182g,0.55mol,1.0eq) and 1200mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (230mL,2.5M,0.57mol,1.04eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (135g,0.60mol,1.04eq) is added, stirring is maintained for 1h, nitrobenzene (74g,0.60mol,1.04eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 900mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the aqueous phase was separated, extracted with 400mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were then filtered and dried by suction to give 81.8g of solid (H-2) in 73% yield.

(3) Preparation of intermediate (J-2)

Under the protection of nitrogen, adding an intermediate (H-2) (81.8g,0.20mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (200mL,2.5M,0.50mol,2.5eq), keeping the reaction for 2H after the addition is finished, slowly adding diphenylphosphonic chloride (104g,0.44mol,2.2eq), stirring for 5H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. 850mL of water is added dropwise to quench the reaction, 600mL of ethyl acetate is added, the phases are separated, the organic phase is washed with 1500mL of saturated saline solution, and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 71.7g of intermediate (J-2) as an off-white solid, yield: and 55 percent.

(4) Preparation of Compound (C-2)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-2) (71.7g,0.11mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.25g,0.022mol,0.20eq) and cesium carbonate (71.3g,0.22mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.62g,0.0022mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, the mixture was filtered through celite, 600mL of dichloromethane was added to the filtrate to extract the filtrate, the organic phase was washed with 1000mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 40.2g of the title compound (C-2) as an off-white solid, yield: and 63 percent.

Element classificationAnd (3) analysis: (C)₃₈H₂₈P₂O₂) Theoretical value: c, 78.88; h, 4.88; p, 11.71; o,5.53 found: c, 78.85; h, 4.89; p, 11.72; o, 5.54; MS (ESI) M/z (M +): theoretical value: 578.16, respectively; measured value: 578.34.

example 3

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-3 below:

the synthetic route for the compound of formula C-3 is shown below:

the preparation method of the compound shown as the formula C-3 specifically comprises the following steps:

(1) preparation of intermediate (D-3)

Under nitrogen protection, a 5L four-necked round bottom flask was charged with compound (M-3) (270g,1.0mol,1.0eq), compound (N-3) (122g,1.0mol,1.0eq) and 2500mL of toluene, sodium carbonate (212g,2.0mol,2.0eq) and purified water (360g,20mol,20eq) were added, nitrogen purged for 30mins, tetrakis (triphenylphosphine) palladium (11.5g,0.01mol,0.01eq) was added, the temperature was raised to 110 ℃ for 15h, and the reaction was monitored by HPLC for completion. After filtration through celite, the organic phase was washed with 2000mL of saturated brine and dried over anhydrous sodium sulfate. Reduced pressure distillation to 400mL, dropwise addition of ethanol 2000mL of solid, majority of the reaction product was separated, filtered, and dried under vacuum to give 182g of the title compound (D-3) as an off-white solid, in terms of yield: 68 percent.

(2) Preparation of intermediate (F-3)

Under the protection of nitrogen, a 5L dry clean four-mouth round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, 500mL of D-3(182g,0.68mol,1.0eq) tetrahydrofuran solution is slowly dripped, the reaction is maintained for 1h after the addition is finished, and iodine-tetrahydrofuran is slowly drippedThe reaction was maintained for 1h with addition of pyran solution (172g iodine/300 ml THF,0.68mol,1.0eq), and then slowly warmed to room temperature and monitored by HPLC for completion. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1200mL of ethanol, and filtered to give 214g (F-3) of a white flaky solid with a yield of 80%.

(3) Preparation of intermediate (H-3)

Under the protection of nitrogen, a 5L dry clean three-neck flask is filled with solid F-3(214g,0.54mol,1.0eq) and 1200mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (240mL,2.5M,0.60mol,1.1eq) is slowly added, the internal temperature is controlled to be below-60 ℃, copper bromide (135g,0.60mol,1.1eq) is added, stirring is maintained for 1h, nitrobenzene (74g,0.60mol,1.1eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 300mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were then filtered and dried by suction to give 90.6g of solid (H-3) in 63% yield.

(4) Preparation of intermediate (J-3)

Under the protection of nitrogen, adding an intermediate (H-3) (90.6g,0.17mol,1.0eq) and 1000mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.5eq), cooling to-70 ℃, slowly dropwise adding n-butyllithium solution (200mL,2.5M,0.50mol,3.0eq), maintaining the reaction for 2H after the addition is finished, slowly dropwise adding diphenylphosphonic chloride (104g,0.44mol,2.6eq), stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction completion by HPLC. And (3) dropwise adding 800mL of water to quench the reaction, adding 300mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 79.1g of intermediate (J-3) as an off-white solid, yield: 60 percent.

(5) Preparation of Compound (C-3)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-3) (79.1g,0.10mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.03g,0.02mol,0.20eq) and cesium carbonate (65.2g,0.20mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.48g,0.002mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, celite was added, the filtrate was extracted with dichloromethane, the organic phase was washed with 1000mL of saturated brine, and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give an off-white solid of 48.7g of the title compound (C-3), yield: 68 percent.

Elemental analysis: (C)₄₈H₃₂P₂O₂) Theoretical value: c, 82.04; h, 4.59; p, 8.82; o,4.55 found: c, 82.07; h, 4.60; p, 8.84; o, 4.55; MS (ESI) M/z (M +): theoretical value: 702.19, respectively; measured value: 702.38.

example 4

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-4 below:

the synthetic route for the compound of formula C-4 is shown below:

the preparation method of the compound shown as the formula C-4 specifically comprises the following steps:

(1) preparation of intermediate (D-4)

Under nitrogen protection, a 5L four-necked round bottom flask was charged with compound (M-3) (270g,1.0mol,1.0eq), compound (N-4) (172g,1.0mol,1.0eq) and 2500mL of toluene, sodium carbonate (212g,2.0mol,2.0eq) and purified water (360g,20mol,20eq) were added, nitrogen purged for 30mins, tetrakis (triphenylphosphine) palladium (11.5g,0.01mol,0.01eq) was added, the temperature was raised to 110 ℃ for 15h, and the reaction was monitored by HPLC for completion. After filtration through celite, the organic phase was washed with 2000mL of saturated brine and dried over anhydrous sodium sulfate. The mixture was distilled under reduced pressure to 400mL, 2000mL of ethanol was added dropwise, mostly analyzed, filtered, and dried under vacuum to give 209g of the title compound (D-4) as an off-white solid, in terms of yield: 66 percent.

(2) Preparation of intermediate (F-4)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (70.8g,0.70mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.03eq) is added, the temperature is reduced to-70 ℃ with stirring, 500mL of D-4(209g,0.66mol,1.0eq) tetrahydrofuran solution is slowly dropped, the reaction is maintained for 1h after the addition, an iodine-tetrahydrofuran solution (167g iodine/300 mL of THF,0.66mol,1.0eq) is slowly dropped, the reaction is maintained for 1h after the addition, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 600mL of solution, extracted with 2L of methyl tert-butyl ether, washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1400mL of ethanol, and filtered to give 240g (F-4) of a white flaky solid in 82% yield.

(3) Preparation of intermediate (H-4)

Under the protection of nitrogen, a 5L dry clean three-neck flask is filled with solid F-4(240g,0.54mol,1.0eq) and 1200mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (240mL,2.5M,0.60mol,1.1eq) is slowly added, the internal temperature is controlled to be below-60 ℃, copper bromide (135g,0.60mol,1.1eq) is added, stirring is maintained for 1h, nitrobenzene (74g,0.60mol,1.1eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 900mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 500mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were then filtered and dried by suction to give 101g of solid (H-4) in 59.3% yield.

(4) Preparation of intermediate (J-4)

Under the protection of nitrogen, adding an intermediate (H-4) (101g,0.16mol,1.0eq) and 1000mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (65.0g,0.56mol,3.5eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (192mL,2.5M,0.48mol,3.0eq), keeping the reaction for 2H after the addition is finished, slowly adding diphenylphosphonic chloride (94.5g,0.40mol,2.6eq) again, stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. Adding 900mL of water dropwise to quench the reaction, adding 500mL of ethyl acetate, separating the phases, washing the organic phase with 1500mL of saturated saline solution, and drying with anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 70.1g of intermediate (J-4) as an off-white solid, yield: 50 percent.

(5) Preparation of Compound (C-4)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-4) (70.1g,0.08mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (1.63g,0.016mol,0.20eq) and cesium carbonate (52.1g,0.16mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.18g,0.0016mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 700mL of water, the pH was adjusted to 6 with hydrochloric acid, celite was added, the filtrate was extracted with dichloromethane, the organic phase was washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 41.7g of the title compound (C-4) as an off-white solid, yield: 65 percent.

Elemental analysis: (C)₅₆H₃₆P₂O₂) Theoretical value: c, 83.78; h, 4.52; p, 7.72; o,3.99 found: c, 83.80; h, 4.53; p, 7.75; o, 3.99; MS (ESI) M/z (M +): theoretical value: 802.22; measured value: 802.48.

example 5

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-5 below:

the synthetic route for the compound of formula C-5 is shown below:

the preparation method of the compound shown as the formula C-5 specifically comprises the following steps:

(1) preparation of intermediate (F-5)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, D-5(139.5g,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h, an iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, the organic phase was washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 600mL of ethanol, and filtered to give 182g (F-5) of a white flaky solid with a yield of 81.1%.

(2) Preparation of intermediate (H-5)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with the solid intermediate F-5(182g,0.55mol,1.0eq) and 1400mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (230mL,2.5M,0.57mol,1.04eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (128g,0.57mol,1.04eq) is added, stirring is maintained for 1h, nitrobenzene (71g,0.57mol,1.04eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 400mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were filtered and then dried by suction to obtain 82g of a solid (H-5) with a yield of 72.7%.

(3) Preparation of intermediate (J-5)

Under the protection of nitrogen, adding an intermediate (H-5) (82g,0.20mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.0eq), cooling to-70 ℃, slowly dropwise adding an n-butyllithium solution (200mL,2.5M,0.50mol,2.5eq), maintaining the reaction for 2H after the addition is finished, slowly dropwise adding diphenylphosphonic chloride (104g,0.44mol,2.2eq), stirring for 5H at-70 ℃, slowly heating to room temperature, and monitoring the reaction by HPLC to be complete. And adding 800mL of water dropwise to quench the reaction, adding 500mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 71.8g of intermediate (J-5) as an off-white solid, yield: and 55 percent.

(4) Preparation of Compound (C-5)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-5) (71.8g,0.11mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.25g,0.022mol,0.20eq) and cesium carbonate (71.3g,0.22mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.62g,0.0022mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, the mixture was filtered through celite, 600mL of dichloromethane was added to the filtrate to extract the filtrate, the organic phase was washed with 1500mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried under vacuum to give an off-white solid 39.4g of the objective compound (C-5), yield: 62 percent.

Elemental analysis: (C)₃₈H₂₈P₂O₂) Theoretical value: c, 78.88; h, 4.88; p, 10.71; o,5.53 found: c, 78.86; h, 4.88; p, 10.72; o, 5.54; MS (ESI) M/z (M +): theoretical value: 578.16, respectively; measured value: 578.32.

example 6

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-6 below:

the synthetic route for the compound of formula C-6 is shown below:

the preparation method of the compound shown as the formula C-6 specifically comprises the following steps:

(1) preparation of intermediate (F-6)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, D-6(181.9g,0.68mol,1.0eq) is slowly added dropwise to 400mL of tetrahydrofuran solution, the reaction is maintained for 1h after the addition, iodine-tetrahydrofuran solution (172g iodine/300 mL of THF,0.68mol,1.0eq) is slowly added dropwise, the reaction is maintained for 1h after the addition, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, the organic phase was washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1200mL of ethanol, and filtered to give 212g (F-6) of a white flaky solid with a yield of 79.4%.

(2) Preparation of intermediate (H-6)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with a solid intermediate F-6(212g,0.54mol,1.0eq) and 1500mL of anhydrous ether, the temperature is reduced to-70 ℃, an n-butyl lithium solution (230mL,2.5M,0.57mol,1.05eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (128g,0.57mol,1.05eq) is added, stirring is maintained for 1h, nitrobenzene (70.2g,0.57mol,1.05eq) is added, stirring is maintained at-70 ℃ for 4h, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 400mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were then filtered and dried by suction to give 106g of a solid (H-6) in a yield of 74%.

(3) Preparation of intermediate (J-6)

Under the protection of nitrogen, adding an intermediate (H-6) (106g,0.20mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (200mL,2.5M,0.50mol,2.5eq), maintaining the reaction for 2H after the addition is finished, then slowly adding diphenylphosphonic chloride (104g,0.44mol,2.2eq), stirring for 5H at-70 ℃, slowly heating to room temperature, and monitoring the reaction by HPLC to be complete. And adding 800mL of water dropwise to quench the reaction, adding 500mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 83.8g of intermediate (J-6) as an off-white solid, yield: 54 percent.

(4) Preparation of Compound (C-6)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-6) (83.8g,0.11mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.25g,0.022mol,0.20eq) and cesium carbonate (71.3g,0.22mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.62g,0.0022mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, the mixture was filtered through celite, 500mL of dichloromethane was added to the filtrate to extract the filtrate, the organic phase was washed with 1500mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 44.8g of the title compound (C-6) as an off-white solid in yield: 58 percent.

Elemental analysis: (C)₄₈H₃₂P₂O₂) Theoretical value: c, 82.04; h, 4.59; p, 8.82; o,4.55 found: c, 82.05; h, 4.60; p, 8.81; o, 4.54; MS (ESI) M/z (M +): theoretical value: 702.19, respectively; measured value: 702.38.

example 7

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-7 below:

the synthetic route for the compound of formula C-7 is shown below:

the preparation method of the compound shown as the formula C-7 specifically comprises the following steps:

(1) preparation of intermediate (F-7)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, D-7(164.2g,0.68mol,1.0eq) is slowly dropped into 400mL of tetrahydrofuran solution, the reaction is maintained for 1h after the addition, iodine-tetrahydrofuran solution (172g iodine/300 mL of THF,0.68mol,1.0eq) is slowly dropped into the mixture, the reaction is maintained for 1h after the addition, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, the organic phase was washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1200mL of ethanol, and filtered to give 191g (F-7) of a white flaky solid in 76.4% yield.

(2) Preparation of intermediate (H-7)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with the solid intermediate F-7(191g,0.52mol,1.0eq) and 1200mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (220mL,2.5M,0.55mol,1.05eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (123g,0.55mol,1.05eq) is added, stirring is maintained for 1h, nitrobenzene (67.3g,0.55mol,1.05eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 400mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were then filtered and dried by suction to give 96.2g of solid (H-7) in 77% yield.

(3) Preparation of intermediate (J-7)

Under the protection of nitrogen, adding an intermediate (H-7) (96.2g,0.20mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (200mL,2.5M,0.50mol,2.5eq), keeping the reaction for 2H after the addition is finished, slowly adding diphenylphosphonic chloride (104g,0.44mol,2.2eq), stirring for 5H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. 800mL of water is added dropwise to quench the reaction, 600mL of ethyl acetate is added, the phases are separated, the organic phase is washed by 1500mL of saturated saline solution, and dried by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 78.1g of intermediate (J-7) as an off-white solid, yield: and 55 percent.

(4) Preparation of Compound (C-7)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-7) (78.1g,0.11mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.25g,0.022mol,0.20eq) and cesium carbonate (71.3g,0.22mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.62g,0.0022mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, the mixture was filtered through celite, 600mL of dichloromethane was added to the filtrate to extract the filtrate, the organic phase was washed with 1500mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 36.5g of the title compound (C-7) as an off-white solid in yield: 52 percent.

Elemental analysis: (C)₄₄H₂₈P₂O₂) Theoretical value: c, 81.22; h, 4.34; p, 9.52; o,4.92 found: c, 81.24; h, 4.35; p, 9.51; o, 4.90; MS (ESI) M/z (M +): theoretical value: 650.16, respectively; measured value: 650.42.

example 8

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-8 below:

the synthetic route for the compound of formula C-8 is shown below:

the preparation method of the compound shown as the formula C-8 specifically comprises the following steps:

(1) preparation of intermediate (D-8)

Under nitrogen protection, compound (M-3) (270g,1.0mol,1.0eq), compound (N-8) (198g,1.0mol,1.0eq) and 2500mL of toluene were added to a 5L four-necked round bottom flask, sodium carbonate (212g,2.0mol,2.0eq) and purified water (360g,20mol,20eq) were added, nitrogen purged for 30mins, tetrakis (triphenylphosphine) palladium (11.5g,0.01mol,0.01eq) was added, the temperature was raised to 110 ℃ for 15h, and the reaction was monitored by HPLC for completion. After filtration through celite, the organic phase was washed with 2000mL of saturated brine and dried over anhydrous sodium sulfate. Reduced pressure distillation to 400mL, dropwise addition of ethanol 2000mL of solid, majority of the reaction product was separated, filtered, and dried under vacuum to give 232g of the title compound (D-8) as an off-white solid, yield: 67.5 percent.

(2) Preparation of intermediate (F-8)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, 500mL of D-8(232g,0.675mol,1.0eq) tetrahydrofuran solution is slowly added dropwise, the reaction is maintained for 1h after the addition, iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly added dropwise, the reaction is maintained for 1h after the addition, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1200mL of ethanol, and filtered to give 248g (F-8) of a white flaky solid with a yield of 79%.

(3) Preparation of intermediate (H-8)

Under the protection of nitrogen, 1500mL of solid F-8(214g,0.53mol,1.0eq) and anhydrous ether were charged into a 5L dry clean three-necked flask, the temperature was reduced to-70 ℃, an n-butyllithium solution (240mL,2.5M,0.60mol,1.1eq) was slowly added, the internal temperature was controlled to-60 ℃, copper bromide (135g,0.60mol,1.1eq) was added, stirring was maintained for 1h, nitrobenzene (74g,0.60mol,1.1eq) was added, stirring was maintained at-70 ℃ for 4h, the temperature was slowly increased to room temperature, and the reaction was monitored by HPLC for completion. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 300mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were filtered and then dried by suction to give 112g of a solid (H-8) in a yield of 62%.

(4) Preparation of intermediate (J-8)

Under the protection of nitrogen, adding an intermediate (H-8) (112g,0.16mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (55.8g,0.48mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (160mL,2.5M,0.40mol,2.5eq), keeping the reaction for 2H after the addition is finished, then slowly adding diphenylphosphonic chloride (84g,0.36mol,2.2eq), stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. Adding 800mL of water dropwise to quench the reaction, adding 400mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 92.8g of intermediate (J-8) as an off-white solid, yield: 61 percent.

(5) Preparation of Compound (C-8)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-8) (92.8g,0.10mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.03g,0.02mol,0.20eq) and cesium carbonate (65.2g,0.20mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.48g,0.002mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, celite was added, the filtrate was extracted with dichloromethane, the organic phase was washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 53.8g of the title compound (C-8) as an off-white solid, yield: and 63 percent.

Elemental analysis: (C)₆₀H₄₀P₂O₂) Theoretical value: c, 84.30; h, 4.72; p, 7.25; o,3.47 factMeasuring: c, 84.32; h, 4.73; p, 7.24; o, 3.45; MS (ESI) M/z (M +): theoretical value: 854.25, respectively; measured value: 854.51.

example 9

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-9 below:

the synthetic route for the compound of formula C-9 is shown below:

the preparation method of the compound shown as the formula C-9 specifically comprises the following steps:

(1) preparation of intermediate (D-9)

Under nitrogen protection, a 5L four-necked round bottom flask was charged with compound (M-3) (270g,1.0mol,1.0eq), compound (N-9) (212g,1.0mol,1.0eq) and 2500mL of toluene, sodium carbonate (212g,2.0mol,2.0eq) and purified water (360g,20mol,20eq) were added, nitrogen purged for 30mins, tetrakis (triphenylphosphine) palladium (11.5g,0.01mol,0.01eq) was added, the temperature was raised to 110 ℃ for 15h, and the reaction was monitored by HPLC for completion. After filtration through celite, the organic phase was washed with 2000mL of saturated brine and dried over anhydrous sodium sulfate. Reduced pressure distillation to 400mL, dropwise addition of ethanol 2000mL of solid, majority of analysis, filtration, and vacuum drying gave 239g of the title compound (D-9) as an off-white solid, in yield: 67%.

(2) Preparation of intermediate (F-9)

Under the protection of nitrogen, a 5L dry clean four-mouth round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, 500mL of D-9(239g,0.67mol,1.0eq) tetrahydrofuran solution is slowly dropped, the reaction is maintained for 1h after the addition, iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly dropped, the reaction is maintained for 1h after the addition, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC (high performance liquid chromatography)And (4) completing. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1400mL of ethanol, and filtered to give 261g (F-9) of a white flaky solid with a yield of 80.5%.

(3) Preparation of intermediate (H-9)

Under the protection of nitrogen, 1500mL of solid F-9(261g,0.54mol,1.0eq) and anhydrous ether were charged into a 5L dry clean three-necked flask, the temperature was reduced to-70 ℃, an n-butyllithium solution (240mL,2.5M,0.60mol,1.1eq) was slowly added, the internal temperature was controlled to-60 ℃, copper bromide (135g,0.60mol,1.1eq) was added, stirring was maintained for 1h, nitrobenzene (74g,0.60mol,1.1eq) was added, stirring was continued at-70 ℃ for 4h, the temperature was slowly increased to room temperature, and the reaction was monitored by HPLC for completion. 900mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the aqueous phase was separated, 300mL of ether was used for extraction, the organic phases were combined, the mixture was washed with 1500mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were filtered and then dried by suction to obtain 114g of a solid (H-9) in a yield of 59.3%.

(4) Preparation of intermediate (J-9)

Under the protection of nitrogen, adding an intermediate (H-9) (114g,0.16mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (55.8g,0.48mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (160mL,2.5M,0.40mol,2.5eq), keeping the reaction for 2H after the addition is finished, then slowly adding diphenylphosphonic chloride (84g,0.36mol,2.2eq), stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. Adding 800mL of water dropwise to quench the reaction, adding 400mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 95.6g of intermediate (J-9) as an off-white solid, yield: and 63 percent.

(5) Preparation of Compound (C-9)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-9) (95.6g,0.10mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.03g,0.02mol,0.20eq) and cesium carbonate (65.2g,0.20mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.48g,0.002mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, celite was added, the filtrate was extracted with dichloromethane, the organic phase was washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried under vacuum to give 45.9g of the objective compound (C-9) as an off-white solid, yield: 52 percent.

Elemental analysis: (C)₆₀H₃₆P₄O₂) Theoretical value: c, 81.62; h, 4.11; p, 7.02; o,7.25 found: c, 81.63; h, 4.12; p, 7.02; o, 7.27; MS (ESI) M/z (M +): theoretical value: 882.21, respectively; measured value: 882.45.

example 10

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-10 below:

the synthetic route for the compound of formula C-10 is shown below:

the preparation method of the compound shown as the formula C-10 specifically comprises the following steps:

(1) preparation of intermediate (F-10)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, 400mL of D-10(291g,0.68mol,1.0eq) tetrahydrofuran solution is slowly added dropwise, the reaction is maintained for 1h after the addition, iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly added dropwise, the reaction is maintained for 1h after the addition, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, the organic phase was washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1200mL of ethanol, and filtered to give 217g (F-10) of a white flaky solid in 76% yield.

(2) Preparation of intermediate (H-10)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with the solid intermediate F-10(217g,0.52mol,1.0eq) and 1200mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (220mL,2.5M,0.55mol,1.05eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (123g,0.55mol,1.05eq) is added, stirring is maintained for 1h, nitrobenzene (67.3g,0.55mol,1.05eq) is added, stirring is carried out for 4h at-70 ℃, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 400mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were filtered and then dried by suction to give 116g of a solid (H-10) in 77% yield.

(3) Preparation of intermediate (J-10)

Under the protection of nitrogen, adding an intermediate (H-10) (116g,0.20mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.0eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (200mL,2.5M,0.50mol,2.5eq), maintaining the reaction for 2H after the addition is finished, then slowly adding diphenylphosphonic chloride (104g,0.44mol,2.2eq), stirring for 5H at-70 ℃, slowly heating to room temperature, and monitoring the reaction by HPLC to be complete. 800mL of water is added dropwise to quench the reaction, 600mL of ethyl acetate is added, the phases are separated, the organic phase is washed by 1500mL of saturated saline solution, and dried by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give off-white solid 90.6 intermediate (J-10), yield: and 55 percent.

(4) Preparation of Compound (C-10)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-10) (90.6g,0.11mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.25g,0.022mol,0.20eq) and cesium carbonate (71.3g,0.22mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.62g,0.0022mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, the mixture was filtered through celite, 600mL of dichloromethane was added to the filtrate to extract the filtrate, the organic phase was washed with 1500mL of saturated brine, and the mixture was dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give an off-white solid 42.1g of the title compound (C-10), yield: 51 percent.

Elemental analysis: (C)₅₂H₃₂P₂O₂) Theoretical value: c, 83.19; h, 4.30; p, 8.25; o,4.26 found: c, 83.21; h, 4.30; p, 8.24; o, 4.25; MS (ESI) M/z (M +): theoretical value: 750.19, respectively; measured value: 750.48.

example 11

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-11 below:

the synthetic route for the compound of formula C-11 is shown below:

the preparation method of the compound shown as the formula C-11 specifically comprises the following steps:

(1) preparation of intermediate (F-3)

See example 3.

(2) Preparation of intermediate (E-11)

Under nitrogen protection, compound (M-3) (135g,0.5mol,1.0eq), compound (N-11) (145g,0.5mol,1.0eq) and 1500mL of toluene were added to a 5L four-necked round-bottomed flask, sodium carbonate (106g,1.0mol,2.0eq) and purified water (180g,10mol,20eq) were added, nitrogen purged for 30mins, tetrakis (triphenylphosphine) palladium (6.8g,0.005mol,0.01eq) was added, the temperature was raised to 110 ℃ for 15h, and the reaction was monitored by HPLC for completion. After filtration through celite, the organic phase was washed with 2000mL of saturated brine and dried over anhydrous sodium sulfate. Reduced pressure distillation to 400mL, dropwise addition of 2000mL of ethanol to the solid, majority of the reaction was analyzed, filtered, and dried under vacuum to give 152.2g of the title compound (E-11) as an off-white solid in yield: 70 percent.

(3) Preparation of intermediate (G-11)

Under the protection of nitrogen, a 5L dry clean four-neck round-bottom flask is filled with diisopropylamine (36.4g,0.36mol,1.03eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (140mL,2.5M,0.35mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, 300mL of E-11(152.2g,0.35mol,1.0eq) tetrahydrofuran solution is slowly added dropwise to maintain the reaction for 1h, an iodine-tetrahydrofuran solution (88.5g of iodine/150 mL of THF,0.35mol,1.0eq) is slowly added dropwise to maintain the reaction for 1h, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 400mL of the solution, extracted with 2L of methyl tert-butyl ether, washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 800mL of ethanol, and filtered to give 151G (G-11) of a white flaky solid with a yield of 77.2%.

(4) Preparation of intermediate (H-11)

Under the protection of nitrogen, a 5L dry clean three-neck flask is filled with solid F-3(107G,0.27mol,1.0eq), solid G-11(151G,0.27mol,1.0eq) and 1200mL of anhydrous ether, the mixture is fully stirred, the temperature is reduced to-70 ℃, an n-butyl lithium solution (240mL,2.5M,0.60mol,1.1eq) is slowly dropped, the internal temperature is controlled to be-60 ℃, copper bromide (135G,0.60mol,1.1eq) is added, the stirring is maintained for 1h, nitrobenzene (74G,0.60mol,1.1eq) is added, the mixture is stirred for 4h at-70 ℃, the temperature is slowly raised to room temperature, and the reaction is monitored by HPLC to be complete. 800mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the mixture was separated, the aqueous phase was extracted with 300mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were filtered and then dried by suction to obtain 119g of a solid (H-11) in a yield of 63%.

(5) Preparation of intermediate (J-11)

Under the protection of nitrogen, adding an intermediate (H-11) (119g,0.17mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (69.8g,0.60mol,3.5eq), cooling to-70 ℃, slowly adding an n-butyllithium solution (200mL,2.5M,0.50mol,3.0eq), keeping the reaction for 2H after the addition is finished, then slowly adding diphenylphosphonic chloride (104g,0.44mol,2.6eq), stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction to be complete by HPLC. And (3) dropwise adding 800mL of water to quench the reaction, adding 300mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give an off-white solid 94.2g of intermediate (J-11), yield: 59 percent.

(6) Preparation of Compound (C-11)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-11) (94.2g,0.10mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.03g,0.02mol,0.20eq) and cesium carbonate (65.2g,0.20mol,2.0eq) are added, nitrogen is used for purging for 30mins, then bis (tricyclohexylphosphine) palladium dichloride (1.48g,0.002mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, dichloromethane was added for extraction, and the organic phase was washed with 1500mL of saturated brine and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 50.5g of the title compound (C-11) as an off-white solid in yield: 58 percent.

Elemental analysis: (C)₆₀H₄₁P₂O₂N) theoretical value: c, 82.84; h, 4.75; p, 7.12; o, 3.68; n,1.61 found: c, 82.85; h, 4.74; p, 7.12; o, 3.66; n, 1.63; MS (ESI) M/z (M +): theoretical value: 869.26, respectively; measured value: 869.45.

example 12

This example provides a phosphorus-containing bicyclic compound having the structure shown in formula C-12 below:

the synthetic route for the compound of formula C-12 is shown below:

the preparation method of the compound shown as the formula C-12 specifically comprises the following steps:

(1) preparation of intermediate (D-12)

Under nitrogen protection, compound (M-3) (270g,1.0mol,1.0eq), compound (N-12) (238g,1.0mol,1.0eq) and 2500mL of toluene were added to a 5L four-necked round bottom flask, sodium carbonate (212g,2.0mol,2.0eq) and purified water (360g,20mol,20eq) were added, nitrogen purged for 30mins, tetrakis (triphenylphosphine) palladium (11.5g,0.01mol,0.01eq) was added, the temperature was raised to 110 ℃ for 15h, and the reaction was monitored by HPLC for completion. After filtration through celite, the organic phase was washed with 2000mL of saturated brine and dried over anhydrous sodium sulfate. Reduced pressure distillation to 400mL, dropwise addition of ethanol 2000mL of solid mostly analyzed, filtration, and vacuum drying to give 257g of the title compound (D-12) as an off-white solid, yield: 67%.

(2) Preparation of intermediate (F-12)

Under the protection of nitrogen, a 5L dry clean four-neck round bottom flask is filled with diisopropylamine (72.8g,0.72mol,1.06eq) and 1500mL of anhydrous tetrahydrofuran, the temperature is reduced to-70 ℃, n-butyl lithium solution (272mL,2.5M,0.68mol,1.0eq) is added, the mixture is stirred and cooled to-70 ℃, 500mL of D-12(257g,0.67mol,1.0eq) tetrahydrofuran solution is slowly added dropwise, the reaction is maintained for 1h after the addition, iodine-tetrahydrofuran solution (172g iodine/300 mL THF,0.68mol,1.0eq) is slowly added dropwise, the reaction is maintained for 1h after the addition, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. With 5% Na₂S₂O₃The reaction was quenched with 500mL of the solution, extracted with 2L of methyl tert-butyl ether, washed with 1500mL of saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to give an oil, recrystallized by adding 1400mL of ethanol, and filtered to give 275g (F-12) of a white flaky solid with a yield of 80%.

(3) Preparation of intermediate (H-12)

Under the protection of nitrogen, a 5L dry clean three-neck round-bottom flask is filled with solid F-12(275g,0.54mol,1.0eq) and 1500mL of anhydrous ether, the temperature is reduced to-70 ℃, n-butyl lithium solution (240mL,2.5M,0.60mol,1.1eq) is slowly added, the internal temperature is controlled to be lower than-60 ℃, copper bromide (135g,0.60mol,1.1eq) is added, stirring is maintained for 1h, nitrobenzene (74g,0.60mol,1.1eq) is added, stirring is maintained at-70 ℃ for 4h, the temperature is slowly increased to room temperature, and the reaction is monitored by HPLC to be complete. 900mL of 12% aqueous ammonia was added, the mixture was stirred for 1 hour, the aqueous phase was separated, extracted with 400mL of diethyl ether, the organic phases were combined, washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to precipitate white crystals, which were filtered and then dried by suction to give 121g of a solid (H-12) in a yield of 59.2%.

(4) Preparation of intermediate (J-12)

Under the protection of nitrogen, adding an intermediate (H-12) (121g,0.16mol,1.0eq) and 1200mL of anhydrous tetrahydrofuran into a 3L three-neck round-bottom flask, stirring and cooling to 0 ℃, adding tetramethylethylenediamine (55.8g,0.48mol,3.0eq), cooling to-70 ℃, slowly dropwise adding an n-butyllithium solution (160mL,2.5M,0.40mol,2.5eq), maintaining the reaction for 2H after the addition is finished, slowly dropwise adding diphenylphosphonic chloride (84g,0.36mol,2.2eq), stirring for 4H at-70 ℃, slowly heating to room temperature, and monitoring the reaction by HPLC to be complete. And adding 800mL of water dropwise to quench the reaction, adding 500mL of ethyl acetate, carrying out phase separation, washing an organic phase by 1500mL of saturated saline solution, and drying by anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with methanol, and dried under vacuum to give 100g of intermediate (J-12) as an off-white solid, yield: and 63 percent.

(5) Preparation of Compound (C-12)

Under the protection of nitrogen, a 2L three-neck round-bottom flask is added with intermediate (J-12) (100g,0.10mol,1.0eq) and 600mL of dimethylacetamide, then pivalic acid (2.03g,0.02mol,0.20eq) and cesium carbonate (65.2g,0.20mol,2.0eq) are added, nitrogen is used for purging for 30mins, bis (tricyclohexylphosphine) palladium dichloride (1.48g,0.002mol,0.02eq) is added, the temperature is raised to 150 ℃ for reaction for 15h, and the reaction is monitored by HPLC to be complete. The reaction mixture was quenched with 800mL of water, the pH was adjusted to 6 with hydrochloric acid, celite was added, the filtrate was extracted with dichloromethane, the organic phase was washed with 1500mL of saturated brine, and dried over anhydrous sodium sulfate. The product solution was concentrated under reduced pressure, filtered and washed with acetonitrile, and dried in vacuo to give 52.3g of the title compound (C-12) as an off-white solid, yield: 56 percent.

Elemental analysis: (C)₆₆H₄₈P₂O₂) Theoretical value: c, 84.78; h, 5.17; p, 6.63; o,3.42 found: c, 84.80; h, 5.15; p, 6.65; o, 3.40; MS (ESI) M/z (M +): theoretical value: 934.31, respectively; measured value: 934.52.

example 13

This embodiment provides an organic electroluminescent device, as shown in fig. 2, which includes an anode 1, a hole injection layer 2, a hole transport layer 3, a light-emitting layer 4, an electron transport layer 5, an electron injection layer 6, and a cathode 7, which are stacked in this order from bottom to top.

An anode in the organic electroluminescent device is made of ITO material; the cathode 7 is made of metal Al;

HAT (CN)6 is selected as the material of the hole injection layer 2, and HAT (CN)6 has the chemical structure shown as follows:

the hole transport layer 3 is made of NPB:

the light-emitting layer 4 is formed by co-doping a host material RH and a guest material RD, and the mass ratio of the doping of the host material RH to the doping of the guest material RD is 100: 5:

the electron transport layer 5 is formed by doping a phosphorus-containing bicyclic compound with a structure shown as a main material formula C-1 and 8-hydroxyquinoline Lithium (LiQ), and the mass ratio of doping is 100: 5:

the material of the electron injection layer 6 is formed by doping the compound with the structure shown in the specification and the electron injection material LiF, and the doping mass ratio is 100: 5:

the specific structure of the organic electroluminescent device is formed as follows: the mass ratio of the anode ITO/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light emitting layer (RH: RD is 100: 5)/electron transport layer (ETL, the mass ratio of the compound represented by formula C-1: LiQ is 100: 5)/electron injection layer (EIL: LiF is 100: 5)/cathode (Al).

According to the organic electroluminescent device, the electron transport layer is a compound shown as a formula C-1, and the compound shown as C-1 is a large conjugated system with an electron-deficient closed loop structure taking a biphenyl diphosphoryl heptatomic ring as a center, so that the effective transmission of electrons on the electron transport layer can be ensured; meanwhile, the compound shown in the formula C-1 has proper HOMO energy level and LUMO energy level, so that the potential barrier which needs to be overcome by injecting electrons from the cathode to the light-emitting layer can be reduced, the effective injection of electrons can be increased, the working voltage of the device can be reduced, and the light-emitting efficiency of the device can be improved.

In the structure shown in the formula C-1, the triplet state energy level is high, so that excitons which are beneficial to the recombination of electrons and holes of the OLED device are limited in a light emitting area of the light emitting layer, and the energy return of the light emitting layer to an adjacent electron transport layer is avoided; meanwhile, the triplet state energy level is improved, the blocking effect on holes is increased, and the holes are effectively retained in the light-emitting layer, so that the recombination probability of electrons and holes is improved, and the light-emitting efficiency of the device is improved.

The compound shown in the formula C-1 has high glass transition temperature, high thermal stability and morphological stability and excellent film forming performance, can avoid crystallization caused by heating in the film forming process or in the working process of an OLED device after film forming, and improves the service performance and the service life of the device.

As an alternative embodiment, the guest light emitting material of the light emitting layer may be any compound selected from the group consisting of compounds represented by formula (C-1) and compounds represented by formula (C-2) to formula (C-12).

As an alternative embodiment, the guest light emitting material of the light emitting layer may also be selected from any other compounds having chemical structures represented by general formula (I) and general formula (II).

Example 14

This example provides an organic electroluminescent device, which differs from that provided in example 13 only in that: the electron transport layer material is selected from the compounds with the following structures:

example 15

example 16

example 17

example 18

This example provides an organic electroluminescent device, which differs from that provided in example 11 only in that: the electron transport layer material is selected from the compounds with the following structures:

example 19

example 20

example 21

example 22

example 23

example 24

comparative example 1

This comparative example provides an organic electroluminescent device, which differs from that provided in example 13 only in that: the main material of the electron transport layer is selected from the following compounds K:

test example 1

1. Determination of glass transition temperature

The phosphorus-containing bicyclic compound materials provided in examples 1 to 12 of the present invention and comparative example 1 were subjected to a glass transition temperature test using a Differential Scanning Calorimeter (DSC) ranging from room temperature to 400 ℃, a temperature rise rate of 10 ℃/min, and a nitrogen atmosphere.

2. The HOMO level of the material of the present invention was measured using Cyclic Voltammetry (CV) using a platinum wire (Pt) as the counter electrode and silver/silver chloride (Ag/AgCl) as the reference electrode using an electrochemical workstation. Under the nitrogen atmosphere, the test is carried out in methylene chloride electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate at the scanning rate of 100mV/s, the potential calibration is carried out by ferrocene, and the absolute energy level of the potential of the ferrocene in the vacuum state is set as-4.8 eV:

3. the LUMO energy level of a material molecule was calculated using the bandgap and HOMO of the material:

wherein the band gap

λ_onsetIs the starting spectral absorbance of the material. The results are shown in Table 1.

TABLE 1

	Glass transition temperature	HOMO(eV)	LUMO(eV)
				Compound C-1	136	-6.01	-2.60
Compound C-2	134	-5.91	-2.59
				Compound C-3	142	-5.82	-2.68
Compound C-4	143	-5.56	-2.67
				Compound C-5	138	-6.08	-2.61
Compound C-6	142	-5.99	-2.64
				Compound C-7	146	-5.62	-2.75
Compound C-8	146	-5.64	-2.74
				Compound C-9	145	-5.67	-2.73
Compound C-10	144	-5.66	-2.72
				Compound C-11	135	-5.58	-2.66
Compound C-12	140	-5.54	-2.72
				Compound K	130	-5.42	-2.58

As can be seen from the data in the table, the glass transition temperature of the compounds provided in examples 1 to 12 is increased compared to compound K, so that the materials have better film-forming properties and chemical stability and are not easy to crystallize; the LUMO energy level is reduced, which indicates that the compound has lower electron affinity and is easy to inject electrons from a cathode; the lowering of the LUMO level also enhances the band gap and the triplet level increases, so that the excitation energy of the material is higher than that of the light-emitting layer, and an exciplex cannot be formed with the light-emitting layer, and energy loss due to electron reflux can be prevented, indicating that the compounds provided in examples 1 to 12 are ideal electron transport materials.

Test example 2

The characteristics of the device such as current, voltage, brightness, light-emitting spectrum and the like are synchronously tested by a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system. The organic electroluminescent devices provided in examples 1 to 12 and comparative example 1 were tested and the results are shown in table 2.

TABLE 2

As can be seen from the data in the table, compared with the device in comparative example 1, the operating voltage of the OLED devices provided in examples 13 to 24 is reduced, and the current efficiency is improved, which indicates that the novel compound provided in the present invention has good electron transport capability as an electron transport material of the OLED device, and can significantly improve the light emitting efficiency of the device, reduce the operating voltage of the device, and improve the performance of the OLED.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims

1. A phosphorus-containing bicyclic compound is characterized by having a structure shown as a formula (I) or a formula (II),

ring A, B is independently selected from

Condensed aromatic of C6-C30A ring, a fused heterocycle from C6 to C30;

wherein R is₁、R₂Independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C1-C30 silyl, C6-C60 aryl or C3-C30 heteroaryl.

2. The phosphorus-containing bicyclic compound of claim 1,

said ring A, B is independently selected from

3. A phosphorus-containing bicyclic compound characterized by having a molecular structure represented by any one of the following:

4. a process for the preparation of phosphorus-containing bicyclic compounds according to any one of claims 1 to 2, wherein the synthesis of the compound of formula (I) comprises:

taking a compound shown in a formula D-I and a compound shown in a formula E-I as initial raw materials, respectively reacting with iodine under an alkaline condition to generate an iodide F-I and an iodide G-I, and performing coupling reaction on the iodide F-I and the iodide G-I to obtain an intermediate compound H-I; forming lithium salt by the intermediate compound H-I under the action of a lithiation reagent, reacting with diphenylphosphonic chloride to obtain an intermediate compound J-I, and closing rings at two sides of the intermediate compound J-I under a catalytic condition to obtain a compound shown in a formula (I);

the synthetic route of the compound shown in the formula (I) is as follows:

the synthesis steps of the compound shown in the formula (II) comprise:

taking a compound shown in a formula D-II and a compound shown in a formula E-II as initial raw materials, respectively reacting with iodine under an alkaline condition to generate an iodide F-II and an iodide G-II, and performing coupling reaction on the iodide F-II and the iodide G-II to obtain an intermediate compound H-II; forming lithium salt by the intermediate compound H-II under the action of a lithiation reagent, reacting with diphenylphosphonic chloride to obtain an intermediate compound J-II, and closing rings at two sides of the intermediate compound J-II under a catalytic condition to obtain a compound shown in a formula (II);

the synthetic route of the compound shown in the formula (II) is as follows:

5. the method according to claim 4, wherein the ring closure is performed in the presence of a Pd reagent.

6. Use of a phosphorus-containing bicyclic compound according to any one of claims 1 to 3 as an organic electroluminescent material.

7. An organic electroluminescent element, wherein at least one functional layer of the organic electroluminescent element comprises the phosphorus-containing bicyclic compound according to any one of claims 1 to 3.

8. The organic electroluminescent device of claim 7, wherein the functional layer is an electron transport layer.

9. The organic electroluminescent device according to claim 8, wherein the functional layer is an electron transport layer, the electron transport layer material comprises a host material and a guest material, and the host material is the phosphorus-containing bicyclic compound.

10. An electronic product comprising the organic electroluminescent device according to any one of claims 7 to 9.